Thermal conductive compositions and methods for their preparation and use

ABSTRACT

Thermal conductive compositions, methods for their preparation, and use are provided, which include, for example, as thermal sinks and other uses.

BACKGROUND

A thermal sink that uses a thermal conductive matrix is one of thecommon requirements for electronic applications to dissipate the heatgenerated during operation of the encapsulated microelectronics in thepolymer matrix. Metals can act as good thermal conductors, however,because they are also good electrical conductors they are not veryuseful as thermal sinks. On the other hand, polymer matrices can act aselectrical insulators but are very poor thermal conductors andaccordingly when the temperature rises the polymer will thermallydecompose and not function as a thermal sink.

Accordingly, there is a need for compositions that can function asthermal sinks with better properties than what are currently available.The present disclosure overcomes at least some, or all of thedisadvantages of previous compositions as well as provides otheradvantages as discussed herein.

SUMMARY

In some embodiments, thermal conductive compositions are provided. Insome embodiments, the thermal conductive compositions comprising leastone of a compound of Formula (I):

-   -   wherein:    -   M is Al, Ga, Si, Ge, In, or Sn;    -   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂,        —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH,        —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂,        —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that        R₁, R₂, R₃, and R₄ are not all H,    -   wherein:    -   X is halo;    -   R₅ is C₁-C₆ alkyl;    -   and a compound of Formula (II):

-   -   wherein:    -   y is about 10 to about 500;    -   R₆ is C₁-C₆ alkyl or halo;    -   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃,        —Si(OR₉)₂CH₂CH₂NH₂, —Si(R₉)₂CH₂CH₂NH₂,    -   —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂,        —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or —CH(═O),        provided that each R₇ are not both H;    -   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;    -   R₉ is C₁-C₆ alkyl; and    -   R₁₀ is C₁-C₆ alkyl or halo.

In some embodiments, the composition is a siloxane polymer cross linkedor cured with a compound of Formula (I) or (II). In some embodiments,the siloxane polymer cured or cross linked with a compound of Formula(I) or (II) has a formula of:

wherein

-   each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and-   each z is independently about 1 to about 100.

In some embodiments, the composition is a polyurethane cross linked witha compound of Formula (I) or (II). In some embodiments, the polyurethanecross linked with a compound of Formula (I) or (II) is a compound ofFormula (III):

-   -   wherein:    -   M is Al, Ga, Si, Ge, In, or Sn;    -   R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,        —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH,        —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂,        —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, —CH(═O);    -   wherein:    -   X is halo;    -   R₅ is C₁-C₆ alkyl; and    -   R₁₁ is a polyurethane chain.

In some embodiments, the composition is a polyolefin copolymerized orgrafted with a compound of Formula (I) or (II). In some embodiments, thecomposition has a formula of:

wherein

-   M is Al, Ga, Si, Ge, In, or Sn; and-   q is about 100 to about 10000.

In some embodiments heat sinks comprising at least one of a compound ofFormula (I) are provided:

-   -   wherein:    -   M is Al, Ga, Si, Ge, In, or Sn;    -   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂,        —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH,        —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂,        —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that        R₁, R₂, R₃, and R₄ are not all H,    -   wherein:    -   X is halo;    -   R₅ is C₁-C₆ alkyl;    -   and a compound of Formula (II):

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo.

In some embodiments, heat transfer systems are provided. In someembodiments, the heat transfer systems comprise at least one heatsource; at least one heat sink; and at least one thermal conductivecomposition comprising at least one of a compound of Formula (I)

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;-   or a compound of Formula (II):

wherein:

-   y is about 10 to about 500-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo,    wherein at least a portion of the thermal conductive composition is    positioned substantially between the heat source and the heat sink    and provides thermal communication between the heat source and heat    sink.

Embodiments disclosed herein provide electronic devices, the electronicdevices at least partially encapsulated by a thermal conductivecomposition comprising at least one of a compound of Formula (I):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;-   and a compound of Formula (II):

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo.

In some embodiments, methods of preparing a polyurethane cross-linkedcompound of Formula (I) or (II) are provided, the methods comprisingcontacting a compound of Formula (I) or Formula (II)

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo,-   with a diisocyanate and a polyol under conditions sufficient to form    a polyurethane cross-linked compound of Formula (I) or (II).

In some embodiments, methods of preparing a siloxane polymer crosslinked or cured with a compound of Formula (I) or (II) are provided, themethod comprising contacting a compound of Formula (I) or (II)

wherein:

-   -   M is Al, Ga, Si, Ge, In, or Sn;    -   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂,        —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH,        —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂,        —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that        R₁, R₂, R₃, and R₄ are not all H,    -   wherein:    -   X is halo;    -   R₅ is C₁-C₆ alkyl;

-   -   wherein:    -   y is about 10 to about 500;    -   R₆ is C₁-C₆ alkyl or halo;    -   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃,        —Si(OR₉)₂CH₂CH₂NH₂, —Si(R₉)₂CH₂CH₂NH₂,    -   —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂,        —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or —CH(═O),        provided that each R₇ are not both H;    -   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;    -   R₉ is C₁-C₆ alkyl; and    -   R₁₀ is C₁-C₆ alkyl or halo,        with a siloxane cyclic monomer or silicone oil in the presence        of a crosslinking agent to form the siloxane polymer cross        linked or cured with a compound of Formula (I) or (II).

In some embodiments, methods of preparing a polyolefin copolymerized orgrafted with a compound of Formula (I) or (II) are provided, the methodscomprising contacting a compound of a compound of Formula (I) or (II)

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —CH₂═CH—, CH₂═CH CH₂—, or    —CH₂═CH(CN),    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently CH₂═CH—, or CH₂═CHCH₂—, or CH₂═CH(CN)—;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo,-   with an olefin monomer under conditions suitable for free radical    polymerization or anionic polymerization.

In some embodiments, methods of preparing a polyolefin grafted with acompound of Formula (I) or (II) are provided, the methods comprisingcontacting a polyolefin with a compound of Formula (I) or (II),

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are —CH₃,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   R₇ is —CH₃;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo,-   in the presence of a peroxide in a reactive extruder.

DETAILED DESCRIPTION

This description is not limited to the particular processes,compositions, or methodologies described, as these may vary. Theterminology used in the description is for the purpose of describing theparticular versions or embodiments only, and it is not intended to limitthe scope of the embodiments described herein. Unless defined otherwise,all technical and scientific terms used herein have the same meanings ascommonly understood by one of ordinary skill in the art. In some cases,terms with commonly understood meanings are defined herein for clarityand/or for ready reference, and the inclusion of such definitions hereinshould not necessarily be construed to represent a substantialdifference over what is generally understood in the art. However, incase of conflict, the patent specification, including definitions, willprevail.

It must also be noted that as used herein and in the appended claims,the singular forms “a”, “an”, and “the” include plural reference unlessthe context clearly dictates otherwise.

As used herein, the term “alkyl” means a saturated or unsaturatedhydrocarbon group which is straight-chained or branched. An unsaturatedalkyl group refers to an alkyl group that contains at least one doublebond, which can also be referred to as an “alkenyl.” The alkyl chain canalso be substituted. An alkyl group can contain from 1 to 24, from 1 to22, from 1 to 20, from 1 to 18, from 1 to 16, from 1 to 14, from 1 to12, from 2 to 20, from 1 to 10, from 2 to 10, from 1 to 8, from 2 to 8,from 1 to 6, from 2 to 6, from 1 to 4, from 2 to 4, from 1 to 3, or 2 or3 carbon atoms. Examples of alkyl groups include, but are not limitedto, methyl (Me), ethyl (Et), propyl (for example, n-propyl andisopropyl), butyl (for example, n-butyl, t-butyl, isobutyl), pentyl (forexample, n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl, 4,4dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl,dodecyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl,3-methyl-1-butyl, 2-methyl-3-butyl, 2-methyl-1-pentyl,2,2-dimethyl-1-propyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl,2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl,2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, and thelike.

As used herein, the phrase “C₁-C₂₄ alkyl, optionally comprising at leastone alkenyl group” refers to a C₁-C₂₄ alkyl carbon chain that can haveat least one alkenyl group located anywhere in the chain. When theC₁-C₂₄ alkyl carbon chain has at least one alkenyl group, the length ofthe C₁-C₂₄ alkyl carbon chain is at least two carbons. When present, thecarbons in the alkenyl group are counted as carbons in the C₁-C₂₄ alkylcarbon chain.

As used herein, the term “alkenyl” means a straight or branched alkylgroup having one or more double carbon-carbon bonds and 2-20 carbonatoms, including, but not limited to, ethenyl, 1-propenyl, 2-propenyl,2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and the like. In someembodiments, the alkenyl chain is from 2 to 24 carbon atoms in length,from 2 to 22 carbon atoms in length, from 2 to 20 carbon atoms inlength, from 2 to 18 carbon atoms in length, from 2 to 16 carbon atomsin length, from 2 to 14 carbon atoms in length, from 2 to 12 carbonatoms in length, from 2 to 10 carbon atoms in length, from 2 to 8 carbonatoms in length, from 2 to 6 carbon atoms in length, or from 2 to 4carbon atoms in length. In some embodiments, the alkenyl group has 1, 2,3, 4, 5, or 6 double bonds.

As used herein, the term “alkenylaryl” refers to an alkenyl groupsubstituted with an aryl group.

As used in this document, terms “comprise,” “have,” and “include” andtheir conjugates, as used herein, mean “including but not limited to.”While various compositions, methods, and devices are described in termsof “comprising” various components or steps (interpreted as meaning“including, but not limited to”), the compositions, methods, and devicescan also “consist essentially of” or “consist of” the various componentsand steps, and such terminology should be interpreted as definingessentially closed-member groups.

Embodiments disclosed herein provide new thermal conductors that canact, for example, as heat sinks.

In some embodiments, a thermal conductive composition is provided. Insome embodiments, the thermal conductive composition includes at leastone of a compound of Formula (I):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;-   or a compound of Formula (II):

wherein:

-   y=about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo.

In some embodiments, y is about 10, about 50, about 100, about 150,about 200, about 250, about 300, about 350, about 400, about 450, about500, or a value between any of these values.

In some embodiments, the metal, M, is Al.

In some embodiments, R₁, R₂, R₃, and R₄ are each independently H, orNH₂, —Si(OR₅)2CH₂CH₂NH₂, Si(OR₅)₃, N(CH₃)₃OH, CH₂CH(O)CH₂, —CH₃,—CH═CH₂, —CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂Cl,CH₂OCN, or —CH(═O). In some embodiments, none of R₁, R₂, R₃, and R₄ areH.

In some embodiments, at least one of R₁, R₂, R₃, and R₄ isSi(R₅)₂CH₂CH₂NH₂, Si(OR₅)₂CH₂CH₂NH₂, or Si(OR₅)₃. In some embodiments,at least one of R₁, R₂, R₃, and R₄ is Si(OR₅)₂CH₂CH₂NH₂, or Si(OR₅)₃.

In some embodiments, R₇ is H, or NH₂, —Si(OR₉)₂CH₂CH₂NH₂, Si(OR₉)₃,—N⁺(CH₃)₃ ⁻OH, CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH₂CH(O)CH₂,—CH═CH—CN, —OCN, —CH₂OH, CH₂Cl, CH₂OCN, or —CH(═O). In some embodiments,R₇ is —Si(R₉)₂CH₂CH₂NH₂.

In some embodiments, the composition is a siloxane polymer cross linkedor cured with a compound of Formula (I) or (II). In some embodiments,the siloxane polymer cured or cross linked with a compound of Formula(I) or (II) has a formula of:

wherein

-   each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and-   each z is independently about 10 to about 1000.

In some embodiments, z is about 10, about 100, about 200, about 300,about 400, about 500, about 600, about 700, about 800, about 900, about1000, or a value between any of these values.

In some embodiments, the composition is a polyurethane cross linked witha compound of Formula (I) or (II). In some embodiments, the polyurethanecross linked with a compound of Formula (I) or (II) is a compound ofFormula (III):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O);    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl; and-   R₁₁ is a polyurethane chain.

In some embodiments, the composition is a polyolefin copolymerized orgrafted with a compound of Formula (I) or (II). In some embodiments, thecomposition has a formula of:

wherein

-   M is Al, Ga, Si, Ge, In, or Sn; and-   q is about 100 to about 10000.

In some embodiments, q is about 100, about 500, about 1000, about 1500,about 2000, about 2500, about 3000, about 3500, about 4000, about 4500,about 5000, about 5500, about 6000, about 6500, about 7000, about 7500,about 8000, about 8500, about 9000, about 9500, about 10000, or a valuebetween any of these values.

In some embodiments, the compositions described herein have a thermalconductivity of about 10 W/(m.K) to about 50 W/(m.K). In someembodiments, the compositions described herein have a thermalconductivity of about 10 W/(m.K), about 20 W/(m.K), about 30 W/(m.K),about 40 W/(m.K), about 50 W/(m.K), or a thermal conductivity betweenany of these values.

Heat sinks are also provided herein. A heat sink is generally a passiveheat exchanger that cools a device by dissipating heat from a systemthat generates heat through its normal function into the surroundingmedium. For example, heat sinks are often used to cool CPUs in acomputer. The compositions described herein can be used as heat sinks,amongst other uses.

Accordingly, in some embodiments, a heat sink is provided, wherein theheat sink comprises at least one of a compound of Formula (I):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;-   or a compound of Formula (II):

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo. In some embodiments, y is about 10,    about 50, about 100, about 150, about 200, about 250, about 300,    about 350, about 400, about 450, about 500, or a value between any    of these values.

In some embodiments of the heat sink, the metal, M, is Al. In someembodiments, R₁ is —CH₃, —CH₂CH₃, or halo. In some embodiments, R₁ isSi(R₅)₂CH₂CH₂NH₂. In some embodiment of the heat sink, R₇ is H, —NH₂,—Si(OR₉)₂CH₂CH₂NH₂, —Si(OR₉)₃, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —CH₃,—CH═CH₂, —CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CHCN, —OCN, —CH₂OH, —CH₂Cl,—CH₂OCN, —CH(═O). In some embodiments, R₇ is —Si(R₉)₂CH₂CH₂NH₂.

In some embodiments, the heat sink comprises a siloxane polymer cured orcross linked with a compound of Formula (I) or (II). In someembodiments, the siloxane polymer cured or cross linked with a compoundof Formula (I) or (II) a formula of:

wherein

-   each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and-   each z is independently about 10 to about 1000.

In some embodiments, z is about 10, about 100, about 200, about 300,about 400, about 500, about 600, about 700, about 800, about 900, about1000, or a value between any of these values.

In some embodiments, the heat sink comprises a polyurethane cross linkedwith a compound of Formula (I) or (II). In some embodiments, thepolyurethane cross linked with a compound of Formula (I) or (II) is acompound of Formula (III):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O);    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl; and-   R₁₁ is a polyurethane chain.

In some embodiments, the heat sink comprises a polyolefin copolymerizedor grafted with a compound of Formula (I) or (II). In some embodiments,the polyolefin copolymerized or grafted with a compound of Formula (I)or (II) has a formula of:

wherein

-   M is Al, Ga, Si, Ge, In, or Sn; and-   q is about 100 to about 10000. In some embodiments, q is about 100,    about 500, about 1000, about 1500, about 2000, about 2500, about    3000, about 3500, about 4000, about 4500, about 5000, about 5500,    about 6000, about 6500, about 7000, about 7500, about 8000, about    8500, about 9000, about 9500, about 10000, or a value between any of    these values.

In some embodiments, the heat sinks described herein are configured tohave a thermal conductivity of about 10 W/(m.K) to about 50 W/(m.K). Insome embodiments, the heatsinks described herein are configured to havea thermal conductivity of about 10 W/(m.K), about 20 W/(m.K), about 30W/(m.K), about 40 W/(m.K), about 50 W/(m.K), or a thermal conductivitybetween any of these values.

In some embodiments, a heat transfer system comprising at least one heatsource; at least one heat sink; and at least one thermal conductivecomposition are provided. In some embodiments, the at least one thermalconductive composition comprises includes at least one of a compound ofFormula (I):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;-   or a compound of Formula (II):

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo;    wherein at least a portion of the thermal conductive composition is    positioned substantially between the heat source and the heat sink    and provides thermal communication between the heat source and heat    sink. In some embodiments, M is Al. In some embodiments, y is about    10, about 50, about 100, about 150, about 200, about 250, about 300,    about 350, about 400, about 450, about 500, or a value between any    of these values.

In some embodiments of the heat transfer system, R₁, R₂, R₃, and R₄ areeach independently H, or NH₂, —Si(OR₅)₂CH₂CH₂NH₂, Si(OR₅)₃, N(CH₃)₃OH,CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CH—CN, —OCN,—CH₂OH, CH₂Cl, CH₂OCN, or —CH(═O).

In some embodiments of the heat transfer system, R₇ is H, or NH₂,—Si(OR₉)₂CH₂CH₂NH₂, Si(OR₉)₃, —N⁺(CH₃)₃ ⁻OH, CH₂CH(O)CH₂, —CH₃, —CH═CH₂,—CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂Cl, CH₂OCN, or—CH(═O).

In some embodiments of the heat transfer system, the thermal conductivecomposition is a siloxane polymer cross linked with a compound ofFormula (I) or (II). In some embodiments, the siloxane polymer cured orcross linked with a compound of Formula (I) or (II) has a formula of:

wherein

-   each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and-   each z is independently about 10 to about 1000.

In some embodiments, z is about 10, about 100, about 200, about 300,about 400, about 500, about 600, about 700, about 800, about 900, about1000, or a value between any of these values.

In some embodiments, electronic devices that are at least partiallyencapsulated by a thermal conductive composition are provided. In someembodiments, the thermal conductive composition comprises at least oneof a compound of Formula (I):

wherein:

-   M is Al, Ga, Si, Ge, In, or Sn;-   R₁, R₂, R₃, and R₄ are each independently —H, or —NH₂, —Si(OR₅)₃,    —Si(OR₅)₂CH₂CH₂NH₂, —Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,    —Si(R₅)₂CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN,    —CH₂OH, CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are    not all H,    wherein:-   X is halo;-   R₅ is C₁-C₆ alkyl;-   or a compound of Formula (II):

wherein:

-   y is about 10 to about 500;-   R₆ is C₁-C₆ alkyl or halo;-   each R₇ is independently —H, or —NH₂, —Si(OR₉)₂, —Si(OR₉)₂CH₂CH₂NH₂,    —Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,    —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or    —CH(═O), provided that each R₇ are not both H;-   R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂;-   R₉ is C₁-C₆ alkyl; and-   R₁₀ is C₁-C₆ alkyl or halo.

In some embodiments, M is Al. In some embodiments, y is about 10, about50, about 100, about 150, about 200, about 250, about 300, about 350,about 400, about 450, about 500, or a value between any of these values.

In some embodiments of the electronic device, the thermal composition isas described above, wherein R₁, R₂, R₃, and R₄ are each independently H,or NH₂, —Si(OR₅)₂CH₂CH₂NH₂, Si(OR₅)₂, N(CH₃)₃OH, CH₂CH(O)CH₂, —CH₃,—CH═CH₂, —CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂Cl,CH₂OCN, or —CH(═O). In some embodiments, R₇ is H, or NH₂,—Si(OR₉)₂CH₂CH₂NH₂, Si(OR₉)₂, —N⁺(CH₃)₃ ⁻OH, CH₂CH(O)CH₂, —CH₃, —CH═CH₂,—CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂Cl, CH₂OCN, or—CH(═O).

In some embodiment of the electronic device, the thermal composition isa siloxane polymer cross linked with a compound of Formula (I) or (II).In some embodiments, the siloxane polymer cured or cross linked with acompound of Formula (I) or (II) has a formula of:

wherein

-   each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and-   each z is independently about 10 to about 1000.

In some embodiments, the electronic device is encapsulated by thecomposition. Examples of electronic devices that can be partially orcompletely encapsulated by the thermal conductive compositions describedherein, include, but are not limited to a semiconductor chip, aconductive wire, an electronic component, or an electronic circuit.However, other types of electronic devices can also be used inconjunctions with the compositions described herein and the types ofdevice should not be limited unless explicitly limited by the presentdescription.

The aza crown ethers of selective metals from group III and IV ofperiodic table can act as nano thermal conductive ingredients to replacecommercial thermal conductive fillers when their structures are presentas aza crown ether compounds, and/or as grafted on polymeric chainsand/or as polymers and copolymers of aza crown ether complexes and or asmaster batch used with commercial polymers or in combination.

Methods of preparing the thermal compositions described herein are alsoprovided. In some embodiments, compounds of Formula (I) or (II) asdescribed herein are contacted with a siloxane cyclic monomer orsilicone oil in the presence of active cross linking agents such as, butnot limited to, CH₃Si(OCH₂CH₃)₃, C₆H₅Si(OCH₃)₃, C₄H₉Si(OCH₃)₃,CH₂(O)CHCH₂Si(OCH₃)₃, and NH₂CH₂CH₂NHCH₂CH₂Si(OCH₃)₃ under conditionssufficient to prepare the polymers described herein. In someembodiments, the compounds of Formula (I) or (II) are contacted with thesiloxane cyclic monomer or the silicone oil in the presence of the crosslinking agent under dry conditions at temperature of about 0-30° C. toform a siloxane polymers. The polymers can then be used as composites,sealants, and for encapsulating products, rubber and others uses asdescribed herein. A non-limiting example of a siloxane cyclic monomer is

The derivative is formed, for example, by anionic ring openingpolymerization of the siloxane cyclic monomer in the presence of anionicinitiators such as, but not limited to LiNH₂, under, for example, dryconditions, in the presence of aprotic solvents. Examples of aproticsolvents include, but are not limited to, tetrahydrofuran, dioxane,trimethylamine, and the like. The reaction can take place at anysuitable temperature, including but not limited to, a temperatures ofabout 0 to 30 C. Other siloxane derivatives can be formed by a compoundof Formula (I) or (II), wherein R₁, R₂, R₃, R₄, and R₇ are eachindependently glycidyl ether groups (for example, such as but notlimited to CH₂(O)CHCH₂—) with about an equivalent weight of an epoxycuring hardener (for example, amine compounds that contain activehydrogen) of the general formula NH₂R₁₂NH₂ wherein R₁₂ is alkenyl,alkenylaryl, aryl or alicyclic. In some embodiments, the reaction takesplace at a temperature range of about 20-30 C. In some embodiments, thereaction includes the addition of at least one phenolic activator.

In some embodiments, the polyurethane cross linked with a compound ofFormula (I) or (II) are prepared by contacting a compound of Formula (I)or (II), wherein R₁, R₂, R₃, R₄ and R₇ respectively as described hereinwith

or other commercial diisocyanate compounds which can also be referred toas toluene-2,4-diisocyanate, and

or HO{—R₁₃—O—C(O)R₁₄-C(O)OR₁₅—O—)_(q)H, wherein R₁₃, R₁₄, or R₁₅ areindependently C₁-C₆ alkyl and q is about 100 to about 1000. Thesecompounds and can also be referred to as a polyol. The structures canalso be referred to as polyether polyol or polyester polyol. Withoutwishing to be bound by any theory, the reaction occurs as the amino azacrown ether complexes act as catalyst and as crosslinking agent. Theproduct that is formed can take shape of the mold.

In some embodiments, the polyolefins are prepared by copolymerizingcompounds of formula (I) or (II), wherein R₁, R₂, R₃, R₄, and R₇ arevinyl groups such as, but not limited to, CH₂═CH—,or CH₂═CH CH₂—, orCH₂═CH(CN)—, with olefin monomers by free radical polymerization oranionic polymerization implementing standard well known procedures.Examples of olefin monomers include, but are not limited to, ethylene,propylene, acrylonitrile, vinylchloride, butadiene, and the like andthose that are described herein.

In some embodiments, the polyolefin are grafted with a compound ofFormula (I) or (II) are prepared by contacting a polyolefin (forexample, polyethylene or polypropylene) with a compound of Formula (I)or (II), wherein R₁, R₂, R₃, R₄, and R₇ are CH₃ in the presence ofdi-t-butyl peroxide in a reactive extruder. Accordingly, the azacrownether complexes can be grafted on the polyolefin chains. In someembodiments, the conditions include performing reactive extrusion, whichcan be performed in the presence of high decomposition temperatureperoxides such as di-butyl peroxide.

The aza crown ether compounds can be prepared according to generally anymethod. Specific examples of making specific species are describedherein. In some embodiments, the methods described herein are modifiedto yield the different species that are desired to be produced accordingto the substituent groups required to be linked with aza crown ether. Insome embodiments, standard procedures are used by contacting thealkylene diamine or its derivatives with trialkyl metals (for example,AlR₃) or metal halides (for example, AlCl₃) under dry or extremely dryconditions. In some embodiments, cyclization to form aza crown ethersand their derivatives include performing the reaction in dilute solutionand/or presence of catalyst as indicated in the examples describedherein.

EXAMPLES Example 1 Preparation of Poly (Aluminium Ethylenediamine) AzaCrown Ether Complexes

A three necked reaction vessel is fitted with a stirrer, a condenserconnected to a drying tube packed with anhydrous calcium chloride, and aseparating funnel equipped with a pressure equalizing tube immersed intoan oil bath that is temperature controlled by a thermostat. The reactionvessel is charged with two moles of 1,2-ethylenediamine. A droppingfunnel is charged with one mole of anhydrous tri-methyl aluminium (TMA).The reaction vessel is flushed with dry nitrogen for 10 minutes, and theTMA is added portion wise from the dropping funnel into the reactionvessel at a controlled temperature of 80° C. within one hour. Thereactants in the reaction vessel are allowed to react overnight.Thereafter, unreacted TMA is separated from the product by addingmethanol and water (1:1 volume ratio) into the reaction vessel todissolve the unreacted TMA. The product is a viscous liquid that easilyseparates from the dissolved TMA. The product is then removed and driedto yield a low molecular weight polymer, which is set aside forcharacterization. The polymer is used as a curing agent for severalcommercial resins as shown in the following examples.

The same reaction procedure is repeated using TMA and ethylene diaminein 1:1 ratio under similar conditions. A solid high molecular weightpolymer is obtained, purified and characterized. The polymer is used ascuring agent for several commercial resins and or transferred to masterbatch.

The polymer that is produced according to this example can berepresented by the formula of:

wherein R₈ is —NH—CH₂(CH₃)CH₂NH₂ and y is about 10 to about 500.

Example 2 Preparation of Methyl Derivatives of Aluminum EthylenediamineAza Crown Ether Complexes

The same reaction set-up used in Example 1 is used in the preparation ofaluminum ethylenediamine methyl derivative aza crown ether. One mole oftrimethylaluminum is added portion wise to six moles of1-methylethylenediamine (excess) at 80° C. The reaction is allowed tocontinue overnight. The obtained aluminum ethylenediamine azacrown ethercomplex is separated purified and characterized and used as a graftingagent to improve thermal conductivity of several commercial polymers.The procedure can be used to prepare a compound of the followingformula:

Example 3 Preparation of Amino Derivatives of Aluminum EthylenediamineAza Crown Ether Complexes (AAEDACE) (Formula (I))

The same reaction procedure and set-up used in Example 2 are implementedreplacing 1-methylethylene diamine by 1-aminoethylenediamine. Theobtained product is used as curing agent or crosslinking agent forseveral commercial resins.

Example 4 Production of Thermal Conductive Epoxy Resin Consisting Poly(Aluminum Ethylenediamine) Aza Crown Ether Complexes (PAEDACE)

100 g of liquid epoxy resin is mixed with 20 g of (PAEDACE), which canbe prepared according to Example 1. The mixed resin is casted in glassdishes treated with silicon grease as a mold release and left overnight.The thermal conductivity of the solid cured discs are evaluated.Parallel sets of epoxy resins cured with ethylene diamine commercialproduct are prepared and evaluated for comparison.

Example 5 A Compound of Formula (III) as a Curing and/or CrosslinkingAgent for Polyurethane, Siloxane and Epoxy Resins

100 g of commercial liquid epoxy resin is mixed with 20 g of (PAEDACE),which can be prepared according to Example 1. The mixed resin is castedin glass dishes treated with silicon grease as mold release and anelectrical circuit is encapsulated in the resin. The fully curedencapsulated samples are evaluated by measuring the break down voltage.Comparative set of encapsulated circuits in commercial epoxy resin curedwith ethylene diamine are also prepared and evaluated for comparison.

Example 6 Preparation of Encapsulated Resin

100 g of commercial liquid epoxy resin is mixed with 20 g of (AAEDACE),which can be prepared according to Example 3. The mixed resin is castedin glass dishes treated with silicon grease as mold release and anelectrical circuit is encapsulated in the resin. The fully curedencapsulated samples are evaluated by measuring the break down voltage.Comparative set of encapsulated circuits in commercial epoxy resin curedwith ethylene diamine are also prepared and evaluated for comparison.

Example 7 Preparation of Encapsulated Electrical Circuit

Commercial polyurethane is prepared by curing 20 g oftoluenediisocyanate with 20 g of polyesterpolyol, and 5 g of (PAEDACE),which can be prepared according to Example 1, and are mixed gently andused in encapsulation of electrical circuits. Pressure is applied toobtain a high density polyurethane encapsulated sample. Similarencapsulated electrical circuit samples in commercial polyurethane areprepared. The two samples are evaluated. The break down voltage ismeasured and higher breakdown voltage is indication of enhanced thermalconductivity. The procedure described herein can be modified byreplacing PAEDACE with AAEDACE.

Example 8 Preparation of an Encapsulated Electrical Circuit in ThermalConductive Silicon Rubber

One mole of siloxane cyclic monomer is mixed with 0.1 mole of (PAEDACE),which can be prepared according to Example 1 in the presence of 0.01mole of butyl-tris(glycidylether)siloxane as a crosslinking agent. Theobtained resin is poured into a mold containing an electrical circuit.The sample is left to cure overnight and is evaluated via measuring thebreakdown voltage. A similar sample is prepared by using commercialcomposition for silicon rubber. The sample is evaluated for comparison.It is expected that the material used herein performs better than thecommercial composition for silicon rubber.

Specifically, a semiconductor chip is at least partially encapsulated by

wherein z is 50, which can act to dissipate the heat away from thesemiconductor chip. The composition can be prepared by contacting

where the compound is formed by anionic ring opening polymerization ofthe siloxane cyclic monomer as described herein. The procedure can alsobe modified by replacing PAEDACE with AAEDACE.

Example 9 Preparation of Thermal Conductive Polypropylene Based on(PAEDACE)

100 g of (PAEDACE) and (AAEDACE) prepared in according to Examples 1 and3, respectively, are transferred to a 50% master batch implementing highmelt flow rate polypropylene or polyethylene and extruder. Commercialpolypropylene pellets are mixed with 10% thermal conductive master batchbased on PAEDACE and extruded to produce electronic cartridges. Similarcartridges are produced from commercial poly propylene and evaluated forcomparison.

Example 10 Preparation of Thermal Conductive Polypropylene Based on(MAEDACE)

100 g of (MAEDACE), prepared according to Example 2, are transferred to50% master batch implementing high melt flow rate polypropylene.Polypropylene pellets were mixed the (MAEDACE) master batch by 10% and0.05% benzoyl peroxide and extruded to the final objects using reactiveextruder. The produced electronic cartridges contain grafted (MAEDACE)on the polypropylene chains having the following chemical structure areevaluated and compared with commercial polypropylene:

wherein q is about 100 to about 10000.

These examples demonstrate that the compositions and materials describedherein can provide for superior thermal sinks with better propertiesthan what are currently available. The superior properties could nothave been predicted.

What is claimed is:
 1. A thermal conductive composition comprising atleast one of a compound of Formula (I):

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O), provided that R₁, R₂, R₃, and R₄ are not all H, wherein: X ishalo; R₅ is C₁-C₆ alkyl; and a compound of Formula (II):

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,—Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or—CH(═O), provided that each R₇ are not both H; R₈ is —NH—CH₂—CH₂—NH₂ orAl(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkyl or halo.
 2. Thethermal conductive composition of claim 1, wherein R₁, R₂, R₃, and R₄are each independently H, or NH₂, —Si(OR₅)2CH₂CH₂NH₂, Si(OR₅)₃,N(CH₃)₃OH, CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH₂CH(O)CH₂,—CH═CH—CN, —OCN, —CH₂OH, CH₂Cl, CH₂OCN, or —CH(═O).
 3. The thermalconductive composition of claim 1, wherein R₇ is H, or NH₂,—Si(OR₉)₂CH₂CH₂NH₂, Si(OR₉)₃, —N⁺(CH₃)₃ ⁻OH, CH₂CH(O)CH₂, —CH₃, —CH═CH₂,—CH₂CH═CH₂, —CH₂CH(O)CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂Cl, CH₂OCN, or—CH(═O).
 4. The thermal conductive composition of claim 1, wherein thecomposition is a siloxane polymer cross linked or cured with a compoundof Formula (I) or (II).
 5. The thermal conductive composition of claim4, wherein the siloxane polymer cured or cross linked with a compound ofFormula (I) or (II) has a formula of:

wherein each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and each zis independently about 1 to about
 100. 6. The thermal conductivecomposition of claim 1, wherein the composition is a polyurethane crosslinked with a compound of Formula (I) or (II).
 7. The thermal conductivecomposition of claim 6, wherein the polyurethane cross linked with acompound of Formula (I) or (II) is a compound of Formula (III):

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O); wherein: X is halo; R₅ is C₁-C₆ alkyl; and R₁₁ is apolyurethane chain.
 8. The thermal conductive composition of claim 1,wherein the composition is a polyolefin copolymerized or grafted with acompound of Formula (I) or (II).
 9. The thermal conductive compositionof claim 8, wherein the composition has a formula of:

wherein M is Al, Ga, Si, Ge, In, or Sn; and q is about 100 to about10000.
 10. A heat sink comprising at least one of a compound of Formula(I)

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O), provided that R₁, R₂, R₃, and R₄ are not all H, wherein: X ishalo; R₅ is C₁-C₆ alkyl; and a compound of Formula (II):

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,—Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or—CH(═O), provided that each R₇ are not both H; R₈ is —NH—CH₂—CH₂—NH₂ orAl(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkyl or halo.
 11. Theheat sink of claim 10, wherein R₇ is H, —NH₂, —Si(OR₉)₂CH₂CH₂NH₂,—Si(OR₉)₃, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —CH₃, —CH═CH₂, —CH₂CH═CH₂,—CH₂CH(O)CH₂, —CH═CHCN, —OCN, —CH₂OH, —CH₂Cl, —CH₂OCN, —CH(═O).
 12. Theheat sink of claim 10, wherein the composition is a siloxane polymercured or cross linked with a compound of Formula (I) or (II).
 13. Theheat sink of claim 12, wherein the siloxane polymer cured or crosslinked with a compound of Formula (I) or (II) a formula of:

wherein each R₁₂ is alkenyl, alkenylaryl, aryl or alicyclic; and each zis independently about 10 to about
 1000. 14. The heat sink of claim 10,wherein the composition is a polyurethane cross linked with a compoundof Formula (I) or (II).
 15. The heat sink of claim 14, wherein thepolyurethane cross linked with a compound of Formula (I) or (II) is acompound of Formula (III):

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O); wherein: X is halo; R₅ is C₁-C₆ alkyl; and R₁₁ is apolyurethane chain.
 16. The heat sink of claim 10, wherein thecomposition is a polyolefin copolymerized or grafted with a compound ofFormula (I) or (II).
 17. The heat sink of claim 16, wherein thepolyolefin copolymerized or grafted with a compound of Formula (I) or(II) has a formula of:

wherein M is Al, Ga, Si, Ge, In, or Sn; and q is about 100 to about10000.
 18. A heat transfer system or an electronic device: the heattransfer system comprising: at least one heat source; at least one heatsink; and at least one thermal conductive composition comprising atleast one of a compound of Formula (I)

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O), provided that R₁, R₂, R₃, and R₄ are not all H, wherein: X ishalo; R₅ is C₁-C₆ alkyl; or a compound of Formula (II):

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,—Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or—CH(═O), provided that each R₇ are not both H; R₈ is —NH—CH₂—CH₂—NH₂ orAl(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkyl or halo; wherein atleast a portion of the thermal conductive composition is positionedsubstantially between the heat source and the heat sink and providesthermal communication between the heat source and heat sink; or anelectronic device, the electronic device at least partially encapsulatedby a thermal conductive composition comprising at least one of acompound of Formula (I):

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O), provided that R₁, R₂, R₃, and R₄ are not all H, wherein: X ishalo; R₅ is C₁-C₆ alkyl; and a compound of Formula (II):

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,—Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or—CH(═O), provided that each R₇ are not both H; R₈ is —NH—CH₂—CH₂—NH₂ orAl(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkyl or halo.
 19. Amethod of preparing: a polyurethane cross-linked compound of Formula (I)or (II), the method comprising contacting a compound of Formula (I) orFormula (II)

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN,—CH(═O), provided that R₁, R₂, R₃, and R₄ are not all H, wherein: X ishalo; R₅ is C₁-C₆ alkyl;

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,—Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or—CH(═O), provided that each R₇ are not both H; R₈ is —NH—CH₂—CH₂—NH₂ orAl(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkyl or halo, with adiisocyanate and a polyol under conditions sufficient to form apolyurethane cross-linked compound of Formula (I) or (II); or, asiloxane polymer cross linked or cured with a compound of Formula (I) or(II), the method comprising contacting a compound of Formula (I) or (II)

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R3, and R₄ are eachindependently —H, or —NH₂, —Si(OR₅)₃, —Si(OR₅)₂CH₂CH₂NH₂,—Si(R₅)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂,—Si(R₅)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH,CH₂X, CH₂OCN, —CH(═O), provided that R₁, R₂, R₃, and R₄ are not all H,wherein: X is halo; R₅ is C₁-C₆ alkyl;

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently —H, or —NH₂, —Si(OR₉)₃, —Si(OR₉)₂CH₂CH₂NH₂,—Si(R₉)₂CH₂CH₂NH₂, —N⁺(CH₃)₃ ⁻OH, —CH₂CH(O)CH₂, —Si(R₉)₂CH₂CH(O)CH₂,—CH₃, —CH═CH₂, —CH₂CH═CH₂, —CH═CH—CN, —OCN, —CH₂OH, CH₂X, CH₂OCN, or—CH(═O), provided that each R₇ are not both H; R₈ is —NH—CH₂—CH₂—NH₂ orAl(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkyl or halo, with asiloxane cyclic monomer or silicone oil in the presence of acrosslinking agent to form the siloxane polymer cross linked or curedwith a compound of Formula (I) or (II); or polyolefin copolymerized orgrafted with a compound of Formula (I) or (II), the method comprisingcontacting a compound of a compound of Formula (I) or (II)

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are eachindependently —CH₂═CH—, CH₂═CH CH₂—, or —CH₂═CH(CN), wherein: X is halo;R₅ is C₁-C₆ alkyl;

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; each R₇is independently CH₂═CH—, or CH₂═CHCH₂—, or CH₂═CH(CN)—; R₈ is—NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ is C₁-C₆ alkylor halo, with an olefin monomer under conditions suitable for freeradical polymerization or anionic polymerization; or polyolefin graftedwith a compound of Formula (I) or (II), the method comprising contactinga polyolefin with a compound of Formula (I) or (II),

wherein: M is Al, Ga, Si, Ge, In, or Sn; R₁, R₂, R₃, and R₄ are —CH₃,wherein: X is halo; R₅ is C₁-C₆ alkyl;

wherein: y is about 10 to about 500; R₆ is C₁-C₆ alkyl or halo; R₇ is—CH₃; R₈ is —NH—CH₂—CH₂—NH₂ or Al(R₁₀)₂; R₉ is C₁-C₆ alkyl; and R₁₀ isC₁-C₆ alkyl or halo, in the presence of a peroxide in a reactiveextruder.